Patent GB-806814-A (GB)
Title: A process for the preparation of esters of organic carboxylic acids
IPC: C07C51/10
Filed: 1956-03-27
Abstract: Esters of organic carboxylic acids are prepared by treating an organic carboxylic acid in the liquid phase with carbon monoxide or a gaseous mixture containing carbon monoxide, in the presence of a catalyst, as hereinafter defined, and at elevated temperature.  The catalysts which may be used are: the known hydrogenation catalysts consisting of elements of sub-group Ib (e.g. Ag, Cu), sub-group 5a (e.g. V), sub-group 6a (e.g. Cr, Mo, W), sub-group 7a (e.g. Mn), and group 8 (e.g. Ni, Co, Fe, Pt, Pd, Rh, Ru) in the form of metals, oxides or sulphides; the oxides and carbonates of metals of the second and third groups (e.g. Al2O3, BeO, ZnCO3); silicic acid in combined form (e.g. metal silicates) or in free form (e.g. SiO2, or diatomaceous earths) and other surface catalysts such as bleaching earth, bentonite, fuller's earth and active carbon.  The catalysts can be mounted on carriers or can be activated by means of suitable additions.  Organic carboxylic acids which can be used are straight or branched chain aliphatic acids, such as fatty acids, acids obtained by oxidation of paraffins, and acids obtained by oxidation of products from the oxo-synthesis or the Guerbet reaction; cycloaliphatic, aromatic, or heterocyclic acids such as naphthenic acids, resin acids, benzoic acid, naphthalene carboxylic acids and pyridine carboxylic acids; aliphatic, cycloaliphatic or aromatic polybasic acids.  The carboxylic acids may also be unsaturated and in some cases substituted.  Mixtures of acids may be used to give mixtures of esters.  Instead of carbon monoxide, gaseous mixtures containing carbon monoxide, such as mixtures of carbon monoxide and hydrogen, water gas, producer gas and town gas, may be used.  The process may be effected at normal pressure, but advantageously pressures of 10 to 500 atm., preferably 100 to 250 atm., are used, at elevated temperatures, not usually exceeding 400 DEG  C.  The reaction may be carried out in the presence of solvents or diluents. The products may be used as skin oils, ointment bases, lubricants, leather oiling agents and raw materials for wax compositions.  In examples: (1) lauric acid is reacted with carbon monoxide at 100 atmospheres gauge at 280 DEG  C. in the presence of copper chromate to give dodecyl laurate; (2) hydrostearic acid, obtained by hardening commercial oleic acid, is similarly converted to a mixture of cetyl palmitate, cetyl stearate, stearyl palmitate and stearyl stearate; (3) coconut oil fatty acids are similarly converted to a mixture of wax esters; (4) acids obtained by oxidation of paraffin are converted to a mixture of wax esters in the presence of copper silicate; (5) coconut oil fatty acids are converted to esters by reaction with producer gas or water gas at 260 DEG  C. and 150 atm. gauge in the presence of Raney-cobalt; (6) butyric acid is reacted with carbon monoxide as in (1) in the presence of bleaching earth to give butyl butyrate; (7) benzoic acid is reacted as in (1) with CO in the presence of copper chromite to give benzyl benzoate; decahydronaphthalene may be used as a solvent; (8) a mixture of 9-and 10-ketostearic acids is heated with CO at 270-300 DEG  C. and under 150 atm. gauge in the presence of MoS2 to yield a practically colourless wax; (9) octyloxyacetic acid and a nickel-containing hydrogenation catalyst are heated at 280 DEG  C. for 8 hours under a CO pressure of 200 atm. gauge to give octyloxethyl-octyloxyacetate; (10) commercial oleic acid mixed with activated carbon is heated at 280 DEG  C. under 100 atm. excess pressure of CO for 8 hours to give an ester product.